JPH06222495A - Silver halide photosensitive material and image forming method using the same - Google Patents

Abstract

PURPOSE:To enable a high-contrast image to be formed with a developer low in pH by incorporating a specified compound and a specified sensitizing dye in an emulsion layer and a hydrazine compound in the emulsion layer or a hydrophilic colloidal layer. CONSTITUTION:The emulsion layer contains the compound represented by formulae I and II and the sensitizing dye represented by formula III and the emulsion layer or another hydrophilic colloidal layer contains the hydrazine compound represented by formula IV. In I-IV, each of R<1>-R<4> is H or a univalent group; R is an alkyl; Z is a nonmetallic atomic group necessary to form an optionally substituted thiazole, selenazole, oxazole, or pyridine ring; Q is a nonmetallic atomic group necessary to form a 5-membered hetero ring; m is 1 or 2; both of A1 and A2 is H or one of them is H and the other is an acyl or the like; R1 is an aliphatic or aromatic group or the like; G1 is-CO-or the like; G2 is a simple bond or the like; and R2 is H or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material for plate-making, which is used in the field of photolithography and has extremely hard photographic characteristics, and an image forming method thereof.

[0002]

2. Description of the Related Art In the field of graphic arts, an image showing a super-high contrast photographic characteristic in which an image portion and a non-image portion are clearly distinguished in order to improve reproduction of a dot image and a character line image. A forming system is needed.
As one of the methods for rapidly forming a super-high contrast image by using a processing liquid having good storage stability, US Pat.
66,742, 4,168,977, 4,22
1,857, 4,224,401, 4,24
No. 3,739, No. 4,272,606, No. 4,31
The methods described in No. 1,781, No. 4,650,746 and the like are presented. In this method, a surface latent image type silver halide light-sensitive material containing a specific hydrazine derivative compound is added to a pH 11.0 to 1 containing a high concentration of a sulfite preservative.
It is characterized in that a super-high contrast negative image having a γ of more than 10 can be formed by processing with the super-additive developer of 2.3. With this system, it was possible to increase the stability of the developer with a high concentration of sulfite preservative, but in order to obtain a high-contrast image, it is necessary to use a conventional lith developer or rapid processing (rapid access) developer. Higher pH
It is necessary to be a developing solution having a high value, and since it has a high pH value, it cannot be said that it is easily oxidized by air and has sufficient stability. By processing a silver halide light-sensitive material containing a hydrazine compound with a developer having a lower pH value,
Some attempts have been made to create a tough image.

US Pat. No. 4,269,929, JP-A-6
1-267,759 describes a method of adding a amine compound that promotes the contrast enhancement effect of hydrazine to a developing solution as a method of obtaining a high contrast image with a developing solution having a lower pH value. On the other hand, JP-A-60-179,73
No. 4, No. 61-170, 733, No. 61-270, 7
44, 62-948, 63-234, 244.
No. 2-300,747 and US Pat. No. 4,7.
No. 98,780 discloses various hydrazine derivatives having a high contrast-increasing effect, and efforts have been made to enhance the stability of development processing. In JP-A-1-179,939 and JP-A-1-179,940, a light-sensitive material containing a nucleation accelerator having an adsorption group for silver halide grains and a nucleating agent having an adsorption group is used. , A method of forming a high contrast image by processing with a developer having a pH of 11.0 or less. US Pat. Nos. 4,988,604 and 5,04
Nos. 1,355 and 4,994,365 disclose hydrazine compounds having a repeating unit of ethylene oxide and hydrazine compounds having a pyridinium group.

[0004]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide light-sensitive material capable of forming a high contrast image with a developer having a low pH value of pH 11.0 or less. . A second object of the present invention is to provide a silver halide light-sensitive material which has a good storage stability of the light-sensitive material and has a small change in performance with respect to fluctuations in the processing solution. A third object of the present invention is to provide a silver halide light-sensitive material which causes less black spots.

[0005]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the formula (I) or ( II) and a compound represented by the general formula (II
To provide a silver halide photographic light-sensitive material containing a sensitizing dye represented by I) and containing a hydrazine compound represented by the following general formula (IV) in the emulsion layer or other hydrophilic colloid layers. Achieved by General formula (I)

[0006]

[Chemical 5]

General formula (II)

[0008]

[Chemical 6]

In the formula, R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or a monovalent group. However, R ¹ , R ² , R
^At least one of R ³ and R ⁴ is a hydroxyl group, and at least one of the remaining R ¹ , R ² , R ³ and R ⁴ is —S.
R ⁵ groups, -COOR ⁵ group, -N (R ⁵⁾ R ⁶ group, -OR ⁷
Represents a group, a -CN group or a halogen group. Here, R ⁵ and R ⁶ represent a hydrogen atom or a monovalent group, and R ⁷ represents a monovalent group. Further, any ^{two of} R ¹ , R ² and R ³ may combine to form a ring. General formula (III)

[0010]

[Chemical 7]

In the formula, R is an alkyl group, Z is a non-metal atom group necessary for forming a thiazole ring, a selenazole ring, an oxazole ring, or a pyridine ring, each of which may have a substituent, and Q is a 5-membered member. A nonmetallic atom group necessary for forming a heterocycle of the ring, m represents 1 or 2. General formula (IV)

[0012]

[Chemical 8]

In the formula, A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is an acyl group, an alkyl group or an arylsulfonyl group. R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and further has, as part of its substituent, an adsorption promoting group for silver halide, contains a quaternary ammonium cation, or -O. -(CH ₂ CH ₂ O)
n-, -O- (CH ₂ CH (CH ₃ ) O) n-, or -O- (CH ₂ CH (OH) CH ₂ O) n-
, (N is an integer of 3 or more). G ₁ is -CO- group, -COCO- group, -CS
- _{group, -C (= NG 2 R 2} ) - group, -SO- group, -SO ₂
- group or _{-P (O) (G 2 R} 2), - represents a group. G ₂ is a simple bond, —O— group, —S— group, or —N (R ₂ ).
Represents a group, and R ₂ represents a hydrogen atom, an aliphatic group or an aromatic group. When a plurality of R _2's are present in the molecule, they may be the same or different.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is a gold chloro and sulfur sensitized silver chlorobromide emulsion or silver chloroiodobromide emulsion containing an iridium salt and / or a rhodium salt. (A silver chloride content of 60 mol% or more and a silver iodide content of 2 mol% or less) is used. The silver iodide content is more preferably 0.5 mol% or less.

Using the light-sensitive material of the present invention, a super-high contrast negative image can be formed by a developer having at least the following components having a pH value of 9.6 to 11.0 without using amines. It is possible. (1) Hydroquinone developing agent (2) 3-Pyrazolidone type auxiliary developing agent and / or p-aminophenol type auxiliary developing agent 0.06 mol / liter or less (3) Sulfite ion concentration 0.3 to 0.8 mol / liter

The compounds of the general formulas (I) and (II) used in the present invention will be described in detail. Where R ¹ ,
Examples of the monovalent group of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are preferably alkyl group, aryl group, amino group, hydroxy group, alkoxy group, alkylthio group, carbamoyl group, It represents a halogen atom, a cyano group, a carboxyl group, an alkoxycarbonyl group, a mercapto group, an aryloxy group, an arylthio group, an aryloxycarbonyl group or a heterocyclic group. Alternatively, these groups may be substituted.

The alkyl group represented by R ¹ , R ² , R ³ and R ⁴ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms which may have a ring or a branch. Examples of the unsubstituted alkyl group are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, hexyl group,
A cyclohexyl group, a cyclopentylmethyl group, an octyl group, a dodecyl group, a tridecyl group, and a heptadecyl group. The substituent in the substituted alkyl group is, for example, a monocyclic or bicyclic aryl group, a heterocyclic residue, a halogen atom, a carboxy group, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkoxy group having 20 or less carbon atoms, and a hydroxy group. Examples of the substituted alkyl group include benzyl group, phenethyl group, chloromethyl group, 2-chloroethyl group, trifluoromethyl group, carboxymethyl group and 2-
A carboxyethyl group, a 2- (methoxycarbonyl) ethyl group, an ethoxycarbonylmethyl group, a 2-methoxyethyl group, a hydroxymethyl group, a 2-hydroxyethyl group and the like.

The aryl group represented by R ¹ , R ² , R ³ and R ⁴ is a monocyclic or bicyclic unsubstituted or substituted aryl group. Examples of the unsubstituted aryl group include a phenyl group and a naphthyl group, and examples of the substituent when the aryl group is substituted include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a carboxy group, C2-C6 alkoxycarbonyl group, hydroxy group, C1-C6
And alkoxy groups, and specific examples of the substituted aryl group include p-tolyl group, m-tolyl group, p-chlorophenyl group, p-bromophenyl group, o-chlorophenyl group,
m-nitrophenyl group, p-carboxyphenyl group, o
-Carboxyphenyl group, o- (methoxycarbonyl)
There are phenyl group, p-hydroxyphenyl group, p-methoxyphenyl group, m-ethoxyphenyl group and the like.

The amino groups represented by R ¹ , R ² , R ³ and R ⁴ are --N in the description of the general formulas (I) and (II).
(R ⁵ ) R ^{6 is a} group represented as a group. The amino group may be unsubstituted or substituted, and examples of preferable substituents (examples of monovalent groups of R ⁵ and R ⁶ ) include alkyl groups (eg, methyl group, ethyl group, butyl group). ) And an acyl group (for example, an acetyl group, a methylsulfonyl group, etc.).
Specific examples of the substituted amino group include a dimethylamino group, a diethylamino group, a butylamino group and an acetylamino group.

The alkoxy group and aryloxy group represented by R ¹ , R ² , R ³ and R ⁴ are the groups represented as the —OR ⁷ group in the explanation of the general formulas (I) and (II). Preferred specific examples include a methoxy group, an ethoxy group, a butoxy group, a heptadecyloxy group, a phenoxy group and a p-methoxyphenoxy group.

The mercapto group, alkylthio group and arylthio group represented by R ¹ , R ² , R ³ and R ⁴ are the groups represented by the --SR ⁵ group in the explanation of the general formulas (I) and (II). And a preferred specific example is a mercapto group,
Examples thereof include a methylthio group, an ethylthio group, a butylthio group, a 2-methoxyethylthio group, a 2-sulfoethylthio group, a phenylthio group and a 2-pyridylthio group.

The carbamoyl group represented by R ¹ , R ² , R ³ and R ⁴ may have one or two alkyl groups having 1 to 20 carbon atoms and aryl groups having 2 or less rings as a substituent. . Specific examples of the substituted carbamoyl group include a methylcarbamoyl group, a dimethylcarbamoyl group, an ethylcarbamoyl group and a phenylcarbamoyl group.

The carboxyl group, the alkoxycarbonyl group and the aryloxycarbonyl group represented by R ¹ , R ² , R ³ and R ⁴ are represented by --COOR ⁵ group in the explanation of the general formulas (I) and (II). The group represented, as a preferred specific example, a carboxyl group, a methoxycarbonyl group,
Examples include an ethoxycarbonyl group, a butoxycarbonyl group, a phenoxycarbonyl group.

Specific examples of the halogen atom represented by R ¹ , R ² , R ³ and R ⁴ are a fluorine atom, a chlorine atom and a bromine atom.

The heterocyclic residue represented by R ¹ , R ² , R ³ and R ⁴ may have a monocyclic ring or a condensed ring of 2 to 3 rings, and specific examples thereof include a furyl group and a pyridyl group. , 2- (3-
Examples thereof include a methyl) benzothiazolyl group and a 1-benzotriazol group.

Examples of the ring formed by R ¹ and R ² or R ² and R ³ include a cyclopentane ring, a cyclohexane ring,
Examples thereof include a cyclohexene ring, a benzene ring, a furan ring, a pyrrolidine ring and a thiophene ring.

When R ⁴ represents a substituted alkyl group, a hetero ring may be used as the substituent, and the substituted alkyl group represented by the following general formula is preferred.

[0028]

[Chemical 9]

R ¹ , R ² and R ³ have the same meanings as described above, and n represents 2 or 4. P and q are 0 or 1
Is.

The groups represented by R ¹ , R ² , R ³ and R ⁴ may be substituted, and preferred examples of the substituents are R ¹ , R ² , R ³ and R ^4. In addition to those listed, nitro group, sulfamoyl group, sulfonamide group, ureido group, urethane group, thioureido group, thiourethane group, sulfo group, alkyl group or arylsulfonyl group and the like can be mentioned. These groups may be further substituted.

Compounds represented by the general formula (I) or (II)
Where R¹, R², R³And R^FourOf the group represented by
At least one is a hydroxyl group, but R¹Or R³But water
It is preferably an acid group. Particularly preferably R¹Is hydroxy
It is a base. Further, compounds represented by the general formulas (I) and (II)
In compound, R¹, R², R³, R^FourWith the rest of
One is -SR^FiveGroup, -COOR^FiveGroup, -N (R^Five) R
⁶Group, -OR⁷Group, --CN group or halogen atom
However, -SR is preferred ^FiveGroup, or -OR⁷Base
It is a case of representing, and particularly preferably -SR^FiveWhen representing a group
Is. Furthermore R^FourIs -SR^FiveGroup or -OR⁷
It is particularly preferred to represent the group. General formula (I) or (II)
Specific examples of the compound represented by are shown below.

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

The compounds of general formula (I) are
w) and Hass, Berichte, 42, 4638 (1907) and 43, 375 (1910).
Year), J. Org. Chem. 24 by Allen et al.
Pp. 796 (1959), Bull. Soc. Chim. Berg., 60 by De Cat and Dormael.
Page 69 (1951) and Re by Cook et al.
It can be easily synthesized by referring to the description of c. Trav. Chem., 69, 343 (1950). The general formula (II)
The compound of J. by Bower and Doyle.
Chem. Soc., 1957, p. 727 and Alle.
It can be easily synthesized by referring to the description of J. Org. Chem., 24, p.

General formula (I) or (II) in the present invention
The compound (1) may be added at any time during the step of preparing a silver halide emulsion, but is preferably added after the completion of chemical ripening. The addition amount is 1 silver halide.
A range of 1 × 10 ⁻⁴ to 1 × 10 ⁻² per mol is preferably used.

Next, the sensitizing dye of the general formula (III) will be described in detail. In the general formula (III), the heterocycle formed by Z includes thiazole, selenazole, oxazole, benzothiazole, benzoselenazole,
Examples thereof include benzoxazole, naphthothiazole, naphthoselenazole, naphthoxazole, pyridine and quinoline ring. These heterocycles may have a substituent,
Examples thereof include a halogen atom, an alkyl group, a halogenated alkyl group, an alkoxy group, a hydroxyl group and an aryl group. Examples of the heterocycle formed by Q include rhodanine, thiohydantoin, thiooxazolidinedione, and thioselenazolidinedione. These heterocycles may have a substituent, and examples thereof include an alkyl group, a sulfoalkyl group, a carboxyalkyl group, a hydroxyalkyl group, an aryl group and a pyridyl group. Specific examples of the alkyl group represented by R include a methyl group, an ethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group,
2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group,
2-hydroxyethyl group and the like. Specific examples of the compound represented by the general formula (III) are shown below.

[0038]

[Chemical 13]

[0039]

[Chemical 14]

The amount of the compound represented by the general formula (III) added is 2 × 10 ^-5 to 1 × per mol of silver halide.
A range of 10 ^-2 mol is preferred. The sensitizing dye represented by the general formula (III) is a known compound.

Next, the hydrazine compound of the general formula (IV) will be described in detail. The aliphatic group represented by R ₁ in the general formula (IV) is preferably one having 5 to 30 carbon atoms, and particularly a straight chain, branched or cyclic alkyl group having 5 to 20 carbon atoms. This alkyl group has a substituent. The aromatic group represented by R ₁ in the general formula (IV) is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocyclic group represented by R ₁ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of N, O, or S atoms,
These may be monocyclic or may form a condensed ring with other aromatic or heterocyclic ring. Examples of the heterocyclic group include those containing a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a perazolyl group, an isoquinolinyl group, a thiazoline group and a benzthiazolyl group. Particularly preferred as R ₁ is an aryl group. The aryl group or heterocyclic group of R ₁ has a substituent.

The aliphatic group, aromatic group or heterocyclic group of R ₁ is substituted, and a preferable substituent is a straight chain,
A branched or cyclic alkyl group (preferably having 1 to 2 carbon atoms)
0, aralkyl group (preferably having 7 to 30 carbon atoms)
), An alkoxy group (preferably having 1 to 30 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 30 carbon atoms), an acylamino group (preferably having 2 to 40 carbon atoms) ), A sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having 1 to 40 carbon atoms), a phosphoric acid amide group (preferably having 1 to 40 carbon atoms), and the like.

The aliphatic group, aromatic group or heterocyclic group of R ₁ or a substituent thereof has an adsorption promoting group on silver halide, contains a quaternary ammonium cation, or -O- (CH ₂ CH ₂ O) n-, -O- (CH ₂ CH (CH ₃ ) O) n-,
Alternatively, it contains a partial structure of -O- (CH ₂ CH (OH) CH ₂ O) n- (where n is an integer of 3 or more). Examples of the adsorption promoting group on silver halide include a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, a triazole group, and a group having a disulfide bond.

As G ₁ , a —CO— group and a —SO ₂ — group are preferred, and a —CO— group is most preferred. A hydrogen atom is preferable as A ₁ and A ₂ .

Among the groups represented by R ₂ in the general formula (IV), a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 2-methanesulfonamidopropyl group) is preferable. , Phenylsulfonylmethyl group, etc., aralkyl group (eg, O-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, O-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2 -Hydroxymethylphenyl group) and the like. R
₂ cleaves portion of G ₁ -R ₂ from the remainder molecule, -G ₁
It may be one that produces a cyclization reaction that produces a cyclic structure containing an atom of the -R ₂ moiety, and examples thereof include those described in JP-A-63-29,751. To be

R _{1 in the} general formula (IV) may have a ballast group, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and examples thereof include an alkyl group, an alkoxy group, a phenyl group,
An alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like are preferably used.

The compounds of the general formula (IV) of the present invention are disclosed, for example, in JP-A-61-213,847 and JP-A-62-260,153.
No. 49-129,536, 56-153,33
6, No. 56-153,342, and U.S. Pat. No. 4,684.
4,604, 3,379,529, 3,62
0,746, 4,377,634, 4,33
2,878, 4,988,604, 4,99
It can be synthesized using the method described in 4,365 or the like.

Examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0049]

[Chemical 15]

[0050]

[Chemical 16]

[0051]

[Chemical 17]

The addition amount of the compound of the general formula (IV) in the present invention is 1 × 10 ⁻⁶ to 1 mol of silver halide.
5 × 10 ^-2 mol is preferably contained, particularly 1 × 10
^The preferable addition amount is in the range of ^{−5 to} 2 × 10 ⁻² mol.

The compounds of the general formula (IV) of the present invention are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), kents (acetone, methyl ethyl ketone), dimethylformamide, It can be used by dissolving in dimethyl sulfoxide, methyl cellosolve and the like. Further, by well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexane, mechanically emulsified dispersion Can also be created and used. Alternatively, the redox compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

As the method for adjusting the silver halide emulsion used in the present invention, various methods known in the field of silver halide emulsions can be used. For example, P.Glafkides
Written by Shimi e Physique Photography (Chimi
et Physique Photographique, ”(Paul Montel, 1976), GFDuffin,“ Photografic Emulsion Chemistr
y) ”(The Focal Press)
Published in 1966), Buell Zelikmann (VL
Zelikman et al) "Making and Coating Photographic Emulsion (Making and C
oating Photographic Emulsion) "(The Focal
It can be prepared by the method described in Press (The Focal Press), 1964, etc.

The halogen composition of the silver halide emulsion used in the present invention is such that silver chloride having a silver chloride content of 60 mol% or more, silver chlorobromide, and chloroiodo are more effective in achieving the object of the present invention. Silver bromide is preferred. The silver iodide content is preferably less than 5 mol%, particularly preferably less than 2 mol%.

The silver halide emulsion used in the present invention is preferably an emulsion containing a rhodium salt or an iridium salt. These heavy metals are mainly used for achieving high contrast and low fog of the emulsion. In particular, it is preferable to use both in combination. The rhodium salt is a rhodium (III) halide compound, a rhodium complex salt having halogen, amine, CN, NO, etc. as a ligand (for example, (NH ₄ ) ₃ RhCl ₆ , K ₃ RhCl ₆ ,, (NH ₄ ) ₃ RhBr ₆ , (N
H ₄ ) ₃ Rh (NO) Cl ₅ etc.). Examples of the iridium salt include IrCl _3, IrCl ₄ , K ₃ IrCl ₆ , K ₂ IrCl ₆ , and (NH ₄ ) ₃ IrCl ₆ . The rhodium salt and iridium salt may be added at any time before the completion of the first ripening at the time of emulsion production, and it is particularly preferable to add them during grain formation. The addition amount is appropriately in the range of 1 × 10 ⁻⁸ mol to 5 × 10 ⁻⁶ mol, and preferably in the range of 5 × 10 ⁻⁸ mol to 1 × 10 ⁻⁶ mol, per mol of silver.

The average grain size of the silver halide used in the present invention is preferably 0.7 μm or less, more preferably 0.1 to 0.5 μm. The particle size distribution is more preferably monodisperse, and the coefficient of variation represented by [(standard deviation of particle size) / (average particle size)] × 100 is 15% or less, more preferably 10% or less. Silver halide grains are regular (regu
lar) is preferable, but those having an irregular crystal form such as a sphere or a plate, or a composite form of these crystal forms may be used.

The method of reacting the water-soluble silver salt (silver nitrate aqueous solution) with the water-soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. As one form of the double jet method, p in the liquid phase where silver halide is produced is used.
A method of keeping Ag constant, that is, a control double jet method can also be used. Grains can also be formed by using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. The control double jet method and the grain forming method using a silver halide solvent are effective means for producing a silver halide emulsion having a regular crystal form and a narrow grain size distribution.

The silver halide emulsion of the present invention is preferably subjected to gold sensitization and sulfur sensitization. The gold sensitizer used in the present invention is various gold salts,
For example, potassium chloroaurite, potassium aurithiocyanate, auric trichloride, and the like. Specific examples are U.S. Pat. Nos. 2,399,083 and 2,642.
No. 361 and the like. As the sulfur sensitizer used in the present invention, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin. Specific examples are US Pat. Nos. 1,574,944 and 2,2.
78,947, 2,410,689, 2,72
8,668, 3,501,313, 3,65
No. 6,955. Preferred sulfur compounds are thiosulfates and thiourea compounds. The preferred amount of gold sensitizer and sulfur sensitizer added is 1 per mol of silver.
It is 0 ^-7 to 10 ^-2 mol, and more preferably 10 ^-5 to 10
^-3 mol. The molar ratio of the gold sensitizer and the sulfur sensitizer is 1: 3 to 3: 1 and more preferably 1: 2 to 2: 1.
Is.

In the silver halide emulsion used in the present invention, in addition to the sensitizing dye of the general formula (III), various spectral sensitizing dyes (for example, cyanine dyes, in combination, for the purpose of imparting desired spectral sensitivity) can be used. Merocyanine dye, etc.) can be added together. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These sensitizing dyes may be used alone, or may be used in combination for the purpose of providing spectral sensitivity depending on the purpose or for the purpose of supersensitization. Supersensitization can also be performed by adding a dye that does not have a spectral sensitizing effect itself or a substance that does not substantially absorb visible light together with the sensitizing dye. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure, Vol. 176, Vol.
43 (issued in December 1978) Page 23, IVs A to J
It is also described in the section. Here, the sensitizing dye may be added at any stage before coating the silver halide emulsion. For example, it is added during the formation of silver halide grains, during physical ripening, during chemical ripening, and in a coating solution of an emulsion prepared for coating. The preferable amount of the sensitizing dye used in the present invention is in the range of 10 ^-6 to 10 ^-1 mol, and particularly preferably 5 × 10 ^-5 to 1 × 10 ^-2, per mol of silver.
It is in the molar range.

The silver halide emulsion layer or other hydrophilic colloid layer of the present invention may contain an amine derivative, an onium salt, a disulfide derivative or a hydroxymethyl derivative as a nucleation accelerator. As the amine derivative, for example, JP-A-60-140,340,
62-50,829, 62-222,241,
62-250,439, 62-280,733.
No. 63-124, 045, 63-133, 14
No. 5, the same 63-286,840 etc. can be mentioned. The onium salt is preferably an ammonium salt or a phosphonium salt. Examples of preferable ammonium salts include JP-A-62-250439.
The compounds described in JP-A-62-280,733 and the like can be mentioned. Further, examples of preferable phosphonium salts include JP-A Nos. 62-167,939 and 62-2.
The compound described in No. 80,733 etc. can be mentioned. Examples of the disulfide derivative include compounds described in JP-A No. 61-198,147. Examples of the hydroxymethyl derivative include, for example, U.S. Patents 4,693,956 and 4,777,118,
Examples thereof include compounds described in EP 231,850 and JP-A-62-50,829.

To the light-sensitive material of the present invention, various dyes such as a pyrazolone benzylidene dye, an ultraviolet absorbing dye and the like can be added for the purpose of preventing halation, preventing irradiation, changing sensitivity and spectral sensitivity characteristics. The amount of these dye compounds added is ⁵ mg to 4 per 1 m ² .
A preferred range is 00 mg, usually 10 mg to 300 mg.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage during storage or photographic processing, or stabilizing photographic performance. That is, azoles (for example, benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, etc. ), Mercaptopyrimidines, mercaptotriazines (eg thioketo compounds such as oxazolinethione), azaindenes (eg triazaindenes, tetraazaindenes, especially 4-hydroxy-substituted-1,
3,3a, 7-tetrazaindenes, pentaazaindenes, etc.), benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives, and many other known antifoggants or stabilizers. Compounds can be added. Among these, preferred are benzotriazoles (for example, 5
-Methylbenzotriazole) and nitroindazoles (eg 5-nitroindazole) and hydroquinone derivatives (eg hydroquinone, methylhydroquinone). Further, these compounds may be contained in the treatment liquid.

The light-sensitive material of the present invention contains an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), An active vinyl compound (1,3,4-
Triacryloyl-hexahydro-s-triazine,
1,3-vinylsulfonyl-2-propanol etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochromic acid, mucophenoxychromic acid etc.), N-carbamoylpyridinium salts, haloamidinium salts (1-
(1-chloro-1-pyridinomethylenepyrrolidinium-2
-Naphthalene sulfonate, etc.) or the like can be used alone or in combination. Among them, JP-A-53-
No. 41, 221, No. 53-57257, No. 59-16.
The active vinyl compounds described in 2,546, etc. and the active halides described in US Pat. No. 3,325,287 are preferably used.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention, a coating aid antistatic agent, slip property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, hardening, sensitization). ) Etc., various surfactants can be added. For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines, silicone polyethylene) Nonionic surfactants such as oxide adducts), glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars: alkyl carboxylates, alkyl sulfones Acid salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate , Carboxy groups such as alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, sulfo groups, Anionic surfactants containing acidic groups such as phospho group, sulfuric acid ester group, phosphoric acid ester group: amphoteric compounds such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides Surfactant: Alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium and other heterocycles No. 4
Cationic surfactants such as primary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. When a surfactant is used as an antistatic agent, a surfactant containing fluorine (for example, US Pat. No. 4,201,586, JP-A-60-
80,849) are preferably used.

The light-sensitive material of the present invention may contain a dispersion of a water-soluble or poorly-soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate,
(Meth) acrylamide, vinyl ester, glycidin (meth) acrylate, acrylonitrile, styrene, etc., alone or in combination, or in combination with acrylic acid, methacrylic acid α, β-unsaturated dicarboxylic acid, styrene sulfonic acid, etc. A polymer as a monomer component can be used in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain a compound having an acid group. Examples of the compound having an acid group include organic acids such as acetic acid salicylate and ascorbic acid, and polymers or copolymers having acid monomers such as acrylic acid, maleic acid and phthalic acid as repeating units. Among these compounds, ascorbic acid is particularly preferable as the low molecular weight compound, and as the high molecular weight compound, an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene are used. Is a water-dispersible latex of the copolymer.

As the binder or protective colloid for the emulsion layer and other hydrophilic colloid layers, it is advantageous to use gelatin such as lime-processed gelatin and acid-processed gelatin, but other hydrophilic colloids can also be used. it can.
For example, gelatin derivative: Graft polymer of gelatin and other polymer: Protein such as albumin and casein: Cellulose derivative such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates: Sugar derivative such as starch derivative: Polyvinyl alcohol, polyacrylic acid Synthetic hydrophilic polymer compounds such as single or copolymers such as polyacrylamide, polymethacrylic acid, polyvinylimidazole, and polyvinylpyrazole can be used.

Other hydrophilic colloid layers other than the silver halide emulsion layer in the present invention include a surface protective layer, an intermediate layer, a filter layer, an antihalation layer and an antistatic layer. The hydrophilic colloid layer such as the surface protective layer may contain a matting agent for the purpose of preventing adhesion and the like. As a matting agent, US Pat.
No. 45, No. 2,992,101, No. 4,142,89
Nos. 4, 4,396,706, homopolymers of polymethylmethacrylate, copolymers of methylmethacrylate and methacrylic acid, fine particles of starch, silica, magnesia oxide, and the like can be used. Further, the surface protective layer is formed of U.S. Pat. Nos. 3,489,576 and 4,043.
Silicone compounds described in 7,958, JP-B-56-
Colloidal silica described in No. 23,139, other paraffin wax, higher fatty acid ester and the like can be added.

For the emulsion layer and other hydrophilic colloid layers, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer. Further, the emulsion layer and other hydrophilic colloid layers have a whitening agent,
It may contain a development accelerator, an antioxidant, a pH adjuster, a thickener, an antistatic agent and the like.

As the support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, etc. can be used. A polyethylene terephthalate film is particularly preferably used. These supports may be subjected to corona treatment by a known method and, if necessary, may be subjected to undercoating treatment by a known method. Further, a waterproof layer containing a polyvinylidene chloride-based polymer may be provided in order to improve so-called dimensional stability, which changes in dimension due to changes in temperature and humidity.

Using the silver halide light-sensitive material of the present invention,
The developer used to obtain a high-contrast negative image has a pH of 9.6 to 11.0, which is lower than that of the developer used in the conventionally known hydrazine contrast developing system.
Particularly, a developing solution having a pH of 10.0 to 10.8 is used.
Moreover, when the silver halide photographic light-sensitive material of the present invention is used, it is not necessary to include an amine compound that promotes the contrast-increasing effect of hydrazine in the developer, and a high-contrast negative image can be obtained with the developer having the above pH value. You can

The developing solution contains 1-phenyl-3-pyrazolidones or p-dihydroxybenzenes as a developing agent.
-Aminophenols as auxiliary developing agents and sulfites as preservatives.

Examples of dihydroxybenzenes as a developing agent include hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromhydroquinone, and 2 , 5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable. As the 1-phenyl-3-pyrazolidones auxiliary developing agent used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4- Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-
3-pyrazolidone, 1-p-aminophenyl-4,4-
Dimethyl-3-pyrazolidone, 1-p-tolyl-4,4
-Dimethyl-3-pyrazolidone, 1-p-tolyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone and the like can be mentioned. Further, as the p-aminophenol-based auxiliary developing agent, N-methyl-p-aminophenol, p-
Aminophenol, N- (β-hydroxyethyl) -p
-Aminophenol, 2-methyl-p-aminophenol, p-benzylaminophenol and the like.
Usually, 0.1 to 0.8 mol / liter of the dihydroxybenzene developing agent is preferably used. The auxiliary developing agent is used in an amount of 0.06 mol / liter or less.

As the sulfite to be added as a preservative, a compound which gives a free sulfite ion, for example, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Formaldehyde sodium bisulfite etc. are mentioned. The amount of sulfite added is preferably in the range of 0.15 to 1.2 mol / liter, and particularly preferably in the range of 0.3 mol / liter.

In order to set the pH value of the developing solution, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate,
Alkaline agents such as sodium silicate and potassium silicate,
pH adjusters and buffers are used. In addition to the above components, as an additive used in the developing solution, compounds such as boric acid and borax: development inhibitors such as sodium bromide, potassium bromide and potassium iodide: mercapto compounds (for example, 1-
Phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc.), indazole compound (5-nitroindazole etc.), benzimidazole compound (e.g. 5-nitrobenzimidazole), triazole compound Organic development inhibitors such as (5-methylbenzotriazole): ethylene glycol, diethylene glycol,
Organic solvents such as triethylene glycol, dimethylformamide, methyl cellosolve, ethanol, methanol: surfactants, chelating agents, color toning agents, water softeners, development accelerators, defoamers, hardeners, silver stain inhibitors, etc. There is.

When the light-sensitive material according to the present invention is developed with the above-mentioned developing solution, the developing temperature is 18 to 50 ° C., preferably 25.
C. to 40.degree. C., development time is 10 seconds to 180 seconds,
It is preferably used in the range of 10 to 60 seconds.

As the fixing agent, in addition to sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, etc., an organic sulfur compound known to be effective as a fixing agent can be used. Among them, sodium thiosulfate is preferable from the viewpoint of fixing speed. The amount of the fixing agent used is 0.1 to 5
A range of mol / liter is preferably used. The fixing solution may contain water-soluble aluminum (for example, aluminum sulfate, aluminum chloride, potassium hydroxide) as a hardening agent. The amount of aluminum salt is usually 0.2-2.
A range of 0 g Al / l is preferably used. The pH of fixing is usually 3.8 or higher, preferably in the range of 4.0 to 5.5, and acetic acid or a dibasic acid (eg tartaric acid, citric acid, sodium citrate, sodium tartrate etc.) is used for pH adjustment. Used. If desired, the fixer may further contain preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, ammonia, sulfuric acid), image-preserving agents (eg, iodide). potassium)
A chelating agent or the like can be included. The fixing temperature and time are the same as in the case of development.

For washing water, an antifungal agent (see, for example, Horiguchi's "Bacterial and Antibacterial Chemistry", Japanese Patent Application No. 60-253,80) is used.
No. 7 compound), a water washing accelerator (such as sulfite),
It may contain a chelating agent or the like. Washing with water is carried out in order to almost completely remove the silver salt dissolved by fixing, and about 2
A range of 10 to 180 seconds at 5 to 50 ° C is preferably used. The range of 30 ° C to 80 ° C is preferably used for drying, and the drying time can be changed appropriately depending on the surrounding conditions.
It is usually 5 seconds to 200 seconds.

The developing-fixing-washing-drying process steps are conveniently carried out by a roller-conveying type automatic developing machine capable of continuously performing the steps, and are methods generally used in the art as effective means. The automatic processor is described in U.S. Pat. Nos. 3,025,779 and 3,545,971.

The present invention will be described in detail below based on examples. Example 1 1.5 × 10 ⁻⁴ mol / liter 1,3-dimethyl-2
Keeping an aqueous gelatin solution containing imidazolidinethione and 7 × 10 ⁻² mol / liter sodium chloride at 40 ° C., and adding a mixed aqueous solution of sodium chloride and sodium bromide (2 × 10 ⁻⁷ mol per mol of silver) Of potassium hexachloroiridate (III) and 3 × 10 ⁻⁷ mol of sodium hexachlororhodium (III)) and an aqueous solution of silver nitrate are mixed and added by the double jet method over 30 minutes,
A silver chlorobromide emulsion (silver bromide content 30 mol%) consisting of monodisperse cubes (coefficient of variation 9.5%) having an average grain size of 0.25 μm was prepared. After completion of grain formation, water was washed by a conventional method to remove soluble salts, gelatin was added, and sodium chloride, sodium bromide and sodium hydroxide were further added to adjust pAg = 7.5 and pH = 6.0. ,
Sodium thiosulfate was added to this emulsion at a concentration of 2 × 1 per mol of silver.
0 ⁻⁵ mol and potassium chloroaurite (3 × 10 ⁻⁵ mol) were added, and chemical sensitization was performed at 60 ° C. for 40 minutes.

After chemical sensitization, the compound of the general formula (I)
1,2,8 selected from the compounds of (II) and 4-hydroxy-6-methyl- as the comparative compound (a)
Emulsions A to D were prepared by adding 1,3,3a, 7-tetrazaindene at 1 × 10 ^-3 mol per mol of silver. To the emulsions A to D, the sensitizing dye of the present invention and the following comparative compound (b) were added in an amount of 4 × 10 ^-4 mol per mol of each silver as shown in Table 1.

[0083]

[Chemical 18]

Further, as shown in Table 1, a hydrazine compound of the general formula (IV) and a hydrazine compound (c) having the following structure as a comparative compound were added.

[0085]

[Chemical 19]

Further, each emulsion contains 4 × 10 4 per mol of silver.
^-4 mol of the mercapto compound represented by (d), 1 × 10 ⁻³ mol of 5-methylbenzotriazole per mol of silver, and the polyethyl acrylate compound described in Production Formula 3 of US Pat. No. 3,525,620. the 1 m ² per 0.8g as a polymer latex, a p- sodium dodecylbenzenesulfonate as a coating aid 1 m ² per 40m
g, 1,3-divinylsulfonyl-2-propanol as a hardening agent was added so as to be 100 mg per 1 m ² . The prepared emulsion had a dye layer having absorption from blue to green on the back surface side and was coated on an undercoated polyethylene terephthalate support in an amount of 3.4 g of silver per 1 m ² . .

[0087]

[Chemical 20]

A gelatin layer was coated as a protective layer on the silver halide emulsion layer. Amount of gelatin of the protective layer is made to be 1 m ² per 1.2g, having an average particle diameter of 3.5μ is in the protective layer as a matting agent adventitious diameter SiO ₂ 40 mg /
m ² , silicone oil 20 mg / m ² , and 60 p-dodecylbenzene sulfonate sodium as a coating aid.
5 mg / m ^{2 of} the fluorine-based surfactant represented by (e)
m ² was included.

[0089]

[Chemical 21]

In this way, the samples 1 to 33 shown in Table 1 were obtained.
It was created.

[0091]

[Table 1]

Each of the prepared samples was stored in a constant temperature and humidity chamber at 40 ° C. and 60% for one day (condition 1) and for three weeks (condition 2), and then subjected to optical sensitometry with tungsten light at 3200 ° K. The wafer was exposed to light for 5 seconds and developed with a developer having the following composition (1) at 34 ° C. for 30 seconds. (For development, FG-7 manufactured by Fuji Photo Film Co., Ltd.
10F automatic processing machine was used. ) GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used as the fixing solution.

Developer Composition (1) Hydroquinone 30.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.2 g Diethylenetriaminepentaacetic acid 2.0 g Diethylene glycol 40.0 g Boric acid 10.0 g Potassium sulfite 85 0.0 g Sodium bromide 6.0 g 5-Methylbenzotriazole 0.2 g 1-Phenyl-5-mercaptotetrazole 20 mg Calcium carbonate 20.0 g Sodium hydroxide and water are added to adjust to pH 10.5 and 1 liter.

For the sample stored at 40 ° C. and 60% for 3 weeks, the developer having the above composition 1 was put in an automatic developing machine, and the film was processed in a standby state at 34 ° C. for 8 hours per day. The same operation (condition 3) was performed using a liquid that was operated without any operation for 3 weeks and the photographic performance and black spots were evaluated.

The results obtained are shown in Table 2.

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

Here, the sensitivity is shown by the relative value of the reciprocal of the exposure amount that gives a density of 1.5. As an index showing the contrast of the image, fo from the point of fog + density 0.3 of the characteristic curve
Connect the point of g + concentration 3.0 with a straight line, and the slope of this straight line is γ
Expressed as a value. That is, γ = (3.0-0.3) / [lo
g (exposure dose giving a density of 3.0) -log (density of 0.
3), and the larger the γ value, the harder the photographic characteristics.

The black spots were evaluated on a scale of 5 by observing the actual portion when treated at 34 ° C. for 30 seconds with a magnifying glass. "5" indicates the best level without black spots, and "1" indicates the worst level where black spots are significantly generated. “3” is the limit level at which the generation of black spots is practically acceptable.

As can be seen from the results in Table 2, pH = 1
The reason why the present invention has a high level of γ value of 10 or more when processed with a developer of 0.5 and has a good level of "4" and "5" even in the processing of condition 3 in the generation of black spots. Only the sample in which the compounds are combined. Samples No. 3, No. 6, No. 1 using the comparative compound (c) as the hydrazine compound
8, No. 21, No. 24, No. 28 and No. 32 are
A high contrast of γ value of 10 or more cannot be achieved. Also,
The sample using the comparative compound (b) as the sensitizing dye shows a contrast of γ value of 10 or more when the hydrazine compound of the present invention is used, but the black spot generation level is from "1" to
It is "3", and both the contrast enhancement and the black spot are incompatible. (Sample N
o. 16, 17 and 33). Further, a sample No. using an emulsion (D) containing 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene instead of the compound represented by the general formula (I) or (II). Similarly, in Nos. 29 to 33, high contrast and black spots are not compatible. In addition, looking at the difference in sensitivity (indicated by ΔlogE in Table 2) when processed under conditions 1 and 2, the sample according to the present invention has a small difference in sensitivity and is stored under the conditions of 40 ° C. and 60%. It can be seen that the photographic performance is stable.

Example 2 Each sample of Example 1 was subjected to the conditions 2 and 3 of Example 1 by attaching a 488 nm interference filter to a xenon flash light source and exposing it for 10 ⁻⁴ seconds. The same results as in Example 1 were obtained.

[Procedure amendment]

[Submission date] April 22, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

[0034]

[Chemical 12]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

Next, the hydrazine compound of the general formula (IV) will be described in detail. The aliphatic group represented by R ₁ in the general formula (IV) is preferably one having 5 to 30 carbon atoms, and particularly a straight chain, branched or cyclic alkyl group having 5 to 20 carbon atoms. This alkyl group has a substituent. The aromatic group represented by R ₁ in the general formula (IV) is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocyclic group represented by R ₁ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of N, O, or S atoms,
These may be monocyclic or may form a condensed ring with other aromatic or heterocyclic ring. Examples of the heterocyclic group include those containing a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazoline group and a benzthiazolyl group. Particularly preferred as R ₁ is an aryl group. The aryl group or heterocyclic group of R ₁ has a substituent.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

[0050]

[Chemical 16]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

[0051]

[Chemical 17]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

The silver halide emulsion layer or other hydrophilic colloid layer of the present invention may contain an amine derivative, an onium salt, a disulfide derivative or a hydroxymethyl derivative as a nucleation accelerator. As the amine derivative, for example, JP-A-60-140,340,
62-50,829, 62-222,241,
62-250,439, 62-280,733.
No. 63-124, 045, 63-133, 14
No. 5, the same 63-286,840 etc. can be mentioned. The onium salt is preferably an ammonium salt or a phosphonium salt. Examples of preferable ammonium salts include JP-A-62-250439.
The compounds described in JP-A-62-280,733 and the like can be mentioned. Further, examples of preferable phosphonium salts include JP-A-61-167,939 and JP-A-62-162.
The compound described in No. 80,733 etc. can be mentioned. Examples of the disulfide derivative include compounds described in JP-A No. 61-198,147. Examples of the hydroxymethyl derivative include, for example, U.S. Patents 4,693,956 and 4,777,118,
Examples thereof include compounds described in EP 231,850 and JP-A-62-50,829.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction content]

As the sulfite to be added as a preservative, a compound which gives a free sulfite ion, for example, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Formaldehyde sodium bisulfite etc. are mentioned. The amount of sulfite added is preferably in the range of 0.15 to 1.2 mol / liter, and particularly preferably in the range of 0.3 to 0.8 mol / liter.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0081

[Correction method] Change

[Correction content]

The present invention will be described in detail below based on examples. Example 1 1.5 × 10 ⁻⁴ mol / liter 1,3-dimethyl-2
Keeping an aqueous gelatin solution containing imidazolidinethione and 7 × 10 ⁻² mol / liter sodium chloride at 40 ° C., and adding a mixed aqueous solution of sodium chloride and sodium bromide (2 × 10 ⁻⁷ mol per mol of silver) Of potassium hexachloroiridate (III) and 3 × 10 ⁻⁷ mol of ammonium hexachlororhodium (III)) and an aqueous solution of silver nitrate are mixed and added by the double jet method over 30 minutes to obtain an average particle size of 0. Silver chlorobromide emulsion consisting of 0.25 μm monodisperse cubes (coefficient of variation 9.5%) (silver bromide content 3
0 mol%) was prepared. After completion of grain formation, water was washed by a conventional method to remove soluble salts, gelatin was added, and sodium chloride, sodium bromide and sodium hydroxide were further added to adjust pAg = 7.5 and pH = 6.0. , To this emulsion sodium thiosulfate 2 per mole of silver
× 10 ^-5 mol, potassium chloroaurite 3 × 10 ^-5
Molar addition was performed and chemical sensitization was performed at 60 ° C. for 40 minutes.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0082

[Correction method] Change

[Correction content]

After chemical sensitization, the compound of the general formula (I)
1,2,8 selected from the compounds of (II) and 4-hydroxy-6-methyl- as the comparative compound (a)
Emulsions A to D were prepared by adding 1,3,3a, 7-tetrazaindene at 1 × 10 ^-3 mol per mol of silver. To the emulsions A to D, the sensitizing dye of the present invention and the following comparative compound (b) were added in an amount of 4 × 10 ⁻⁴ mol per mol of silver as shown in Tables 1 and 2.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0084

[Correction method] Change

[Correction content]

Further, a hydrazine compound of the general formula (IV) and a hydrazine compound (c) having the following structure as a comparative compound were added as shown in Tables 1 and 2.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0088

[Correction method] Change

[Correction content]

A gelatin layer was coated as a protective layer on the silver halide emulsion layer. Amount of gelatin of the protective layer is made to be 1 m ² per 1.2g, an average particle diameter of amorphous SiO ₂ of 3.5μ are in the protective layer as a matting agent 40 mg /
m ² , silicone oil 20 mg / m ² , and 60 p-dodecylbenzene sulfonate sodium as a coating aid.
5 mg / m ^{2 of} the fluorine-based surfactant represented by (e)
m ² was included.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction content]

Thus, the sample 1 shown in Table 1 and Table 2 was obtained.
~ 33 was created.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0092

[Correction method] Change

[Correction content]

[0092]

[Table 2]

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0093

[Correction method] Change

[Correction content]

Each of the prepared samples was stored in a constant temperature and humidity room at 40 ° C. and 60% for one day (condition 1) and for three weeks (condition 2), and then subjected to optical sensitometry with tungsten light at 3200 ° K. The wafer was exposed to light for 5 seconds and developed with a developer having the following composition (1) at 34 ° C. for 30 seconds. (For development, FG-7 manufactured by Fuji Photo Film Co., Ltd.
10F automatic processing machine was used. ) GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used as the fixing solution.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0094

[Correction method] Change

[Correction content]

Developer Composition (1) Hydroquinone 30.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.2 g Diethylenetriaminepentaacetic acid 2.0 g Diethylene glycol 40.0 g Boric acid 10.0 g Potassium sulfite 85 0.0 g Sodium bromide 6.0 g 5-Methylbenzotriazole 0.2 g 1-Phenyl-5-mercaptotetrazole 20 mg Potassium carbonate 20.0 g Sodium hydroxide and water are added to adjust to pH 10.5 and 1 liter.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0095

[Correction method] Change

[Correction content]

For the sample stored at 40 ° C. and 60% for 3 weeks, the developer having the above composition 1 was put in an automatic developing machine, and the film was processed in a standby state at 34 ° C. for 8 hours per day. The same operation (condition 3) was performed using a liquid that was operated without any operation for 3 weeks and the photographic performance and black spots were evaluated.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0096

[Correction method] Change

[Correction content]

The results obtained are shown in Tables 3 and 4.

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0097

[Correction method] Change

[Correction content]

[0097]

[Table 3]

[Procedure 18]

[Document name to be amended] Statement

[Correction target item name] 0098

[Correction method] Change

[Correction content]

[0098]

[Table 4]

[Procedure Amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0101

[Correction method] Change

[Correction content]

As can be seen from the results of Tables 3 and 4, pH
According to the present invention, a high contrast of γ value of 10 or more is obtained by processing with a developing solution of = 10.5, and the generation of black spots is a good level of "4" and "5" even in the processing of condition 3. It is only the sample which combined the compound of. Samples No. 3, No. 6, and Comparative Compound (c) as hydrazine compound
No.18, No.21, No.24, No.28 and No.3
No. 2 cannot achieve high contrast with a γ value of 10 or more.
The sample using the comparative compound (b) as the sensitizing dye shows a contrast of γ value of 10 or more when the hydrazine compound of the present invention is used, but the black spot generation level is "1".
It is "3", and both high contrast and black spots are not compatible. (sample
No. 16, 17 and 33). Further, a sample No. using an emulsion (D) containing 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene instead of the compound represented by the general formula (I) or (II). Similarly, in Nos. 29 to 33, high contrast and black spots are not compatible. In addition, looking at the difference in sensitivity (indicated by ΔlogE in Table 2) when processed under conditions 1 and 2, the sample according to the present invention has a small difference in sensitivity and is stored under the conditions of 40 ° C. and 60%. It can be seen that the photographic performance is stable.

Claims (3)

[Claims] 1. Halogenation of at least one layer on a support
In a silver halide photographic light-sensitive material having a silver emulsion layer,
A compound represented by the general formula (I) or (II) in the emulsion layer.
And a sensitizing dye represented by the general formula (III),
The following general formula in the emulsion layer or other hydrophilic colloid layer
It contains a hydrazine compound represented by (IV)
The characteristic silver halide photographic light-sensitive material. General formula (I)General formula (II)Where R¹, R², R³And R^FourAre hydrogen atoms and
Represents a monovalent group. However, R¹, R², R³, R^FourSmall
At least one is a hydroxyl group, and further R¹, R²,
R³, R^FourAt least one of -SR^FiveGroup, -C
OOR^FiveGroup, -N (R^Five) R⁶Group, -OR⁷Group, --CN group
Alternatively, it represents a halogen group. Where R^FiveAnd R⁶Is water
Represents an elementary atom or a monovalent group, R⁷Represents a monovalent group.
Also R¹, R², R³Any two of the above combine to form a ring
You can do it. General formula (III):In the formula, R may be an alkyl group and Z may have a substituent.
Good thiazole ring, selenazole ring, oxazole ring,
Or a group of non-metal atoms necessary for forming a pyridine ring,
Q is a non-metal atom required to form a 5-membered heterocycle
The group, m represents 1 or 2. General formula (IV):In the formula, A₁, A₂Are both hydrogen atoms or one is hydrogen source
And the other is acyl, alkyl or arylsulfo
Represents a nyl group. R₁Is an aliphatic group, aromatic group or hetero
Represents a ring group, and as a part of the substituent, halogen
Has an adsorption-promoting group for silver halide or quaternary ammonium salt
On-containing or -O- (CH₂CH₂O)_n-, -O- (CH
₂CH (CH₃) O)_n-, Or -O- (CH ₂CH (OH) CH₂O)_n-, (Ta
However, n is an integer containing 3 or more)
It G₁Is a -CO- group, a -COCO- group, a -CS- group,
-C (= NG₂R₂) -Group, -SO- group, -SO₂-Base,
Or -P (O) (G₂R₂) -Represents a group. G₂Is just
A bond, -O- group, -S- group, or -N (R₂)-
Represent, R₂Represents a hydrogen atom, an aliphatic group or an aromatic group.
You Multiple R in the molecule₂Are present, they are the same
It may be the same or different. 2. A silver chlorobromide emulsion or a silver chloroiodobromide emulsion (silver chloride) in which the silver halide emulsion in the silver halide emulsion layer contains an iridium salt and / or a rhodium salt and is gold and sulfur sensitized. Content 60 mol% or more, silver iodide content 2
2. The silver halide photographic light-sensitive material according to claim 1, characterized in that 3. A method of forming a high-contrast negative image by exposing the silver halide light-sensitive material of claim 1 after imagewise exposure to form a high-contrast negative image, wherein the developer does not contain a high-contrast promoting amount of amine, and at least the following: PH with components 9.6 to 1
An image forming method comprising using a super-additive type developing solution of 1.0. (1) hydroquinone developing agent, (2) 3-pyrazolidone type auxiliary developing agent and / or p-aminophenol type auxiliary developing agent 0.06 mol / liter or less, (3) sulfite ion concentration 0.3 to 0.8 mol /liter.